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EP2686390B1 - Branched polyalkylene glycol ethers as de-airing wetting and dispersing agents for aqueous dispersion colors - Google Patents

Branched polyalkylene glycol ethers as de-airing wetting and dispersing agents for aqueous dispersion colors Download PDF

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Publication number
EP2686390B1
EP2686390B1 EP20120708247 EP12708247A EP2686390B1 EP 2686390 B1 EP2686390 B1 EP 2686390B1 EP 20120708247 EP20120708247 EP 20120708247 EP 12708247 A EP12708247 A EP 12708247A EP 2686390 B1 EP2686390 B1 EP 2686390B1
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EP
European Patent Office
Prior art keywords
pigment
comprised
olefinically unsaturated
wetting
pigments
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Not-in-force
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EP20120708247
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German (de)
French (fr)
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EP2686390A1 (en
Inventor
Hendrik Ahrens
Carsten SCHAEFER
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Clariant International Ltd
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Clariant Finance BVI Ltd
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Publication of EP2686390A1 publication Critical patent/EP2686390A1/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • C09D5/027—Dispersing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
    • C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
    • C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
    • C08G65/2624—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups containing aliphatic amine groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D171/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/002—Inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/42—Ethers, e.g. polyglycol ethers of alcohols or phenols
    • C09K23/46—Ethers of aminoalcohols

Definitions

  • the present invention relates to aqueous emulsion paints which contain branched polyalkylene glycol ethers as deaerating wetting agents and dispersants, and to the use of the branched polyalkylene glycol ethers as deaerating wetting and dispersing agents for aqueous emulsion paints.
  • Aqueous emulsion paints contain polymer dispersions, also called binders, latex or polymer emulsions, inorganic white pigments and fillers, as well as auxiliaries such as wetting and dispersing agents, rheology additives, defoamers, preservatives, fungicides, algicides, film-forming aids, solvents and buffer substances.
  • pigment preparations are metered in volumetrically or gravimetrically and distributed homogeneously in the emulsion paint.
  • the spreading can be done by hand by stirring or by means of an electric stirrer or in a paint mixer, z.
  • As a shaker or on a vibrating table also called Inkshaker or Paintshaker.
  • Tinting with pigment preparations containing organic pigments or red pigments often results in streakiness and a disturbed color image due to hue differences.
  • the organic pigments flocculate in the paint and during the drying process, so that the color strength is reduced.
  • When brushing or rolling the pigment agglomerates are separated again, but different degrees, so that it comes to the observed hue differences. In the laboratory this phenomenon is simulated in the rubout test.
  • the rubout test is in the font US 3840383 described.
  • suitable wetting agents are added to the dispersion paints.
  • Nonylphenol ether phosphate esters nonylphenol ethoxylates, alkyl polyethylene glycol ethers, dinonylsulfosuccinate, difunctional propylene oxide / ethylene oxide block polymers (having secondary OH groups), secondary alcohol ethoxylates, and the like.
  • Hydrogenated castor oil ethoxylate with 40 moles of ethylene oxide and dispersing agent for universal ink fountain which can be used as tinting pastes for aqueous emulsion paints as well as for solvent-based alkyd coatings.
  • US 2008/110368 describes a paint formulation of a pigment powder and nonionic surfactants selected from the group of acetylene surfactants, alkylphenol ethoxylates, ethylene oxide / propylene oxide block copolymers, alcohol ethoxylates and mixtures thereof.
  • Alkoxylates are already described in the literature for a variety of applications and in different chemical compositions. The majority of the alkoxylates described are linear alcohol alkoxylates or linear ethylene oxide / propylene oxide block copolymers.
  • DE-A-10332527 describes the use of polyalkylene oxides to prevent the thickening of protective colloid-stabilized, aqueous polymer dispersions.
  • EP-A-0115926 describes the use of water-soluble polyoxypropylene / polyoxyethylene / polyoxypropylene block copolymers in aqueous metalworking coolants.
  • EP-A-1167452 describes the use of block copolymeric phosphoric acid esters and their salts as pigment wetting agents for pigment pastes, aqueous, solvent-based, low-solvent and solvent-free paints and printing inks.
  • the block copolymers of phosphoric acid are prepared by blockwise reaction of alkylol with styrene oxide, ethylene oxide and optionally with other alkylene oxides and then reacted to the phosphoric acid ester.
  • EP-A-1771520 describes alcohol alkoxylates as low-foaming wetting agents for coating materials consisting of binders, pigments, fillers, additives and solvents.
  • US 4091164 describes ethylene oxide / propylene oxide block copolymers as dispersants for inorganic pigments and fillers in thermoplastics.
  • US 5500219 describes ethylene oxide / propylene oxide block copolymers as dispersants for water-dispersible pesticide granules.
  • US 6083998 describes ethylene oxide / propylene oxide block copolymers as defoamer component for fermentation processes.
  • WO-02/16471 describes alcohol alkoxylates as a dispersant for organic pigment in solvent-based paints.
  • Branched alkoxylates and graft polymers with ethylene oxide / propylene oxide side chains are also described in the literature as wetting and dispersing agents.
  • EP-A-1643833 describes alkanol alkoxylates as penetration promoters and an ethylenediamine alkoxylate derivative as an emulsion stabilizer or as a crystallization inhibitor in crop protection formulations.
  • EP-A-1650246 describes alkoxylated epoxy-amine adducts having a number average molecular weight of more than 500 g / mol, which can be prepared by the reaction of mono- and polyepoxides, primary or secondary amines and alkanolamines and alkylene oxides as wetting and dispersing agents for organic and inorganic pigments and Fillers in pigment preparations.
  • the same document also describes basic polyalkylene oxides based on alkoxylated ethylenediamine as wetting and dispersing agent as prior art.
  • US 4540442 describes ethylenediamine-ethylene oxide / propylene oxide block copolymer as a cleaning component for aqueous paint removal stains.
  • US 5629260 describes the use of branched ethylene oxide / propylene oxide block copolymers as wetting agents for aqueous herbicide solutions.
  • US-A-2007/299228 describes branched ethylene oxide / propylene oxide block copolymers as emulsifiers for aqueous alkyd resin dispersions and aqueous alkyd resin paints.
  • WO-2009/130282 describes the use of alcohol alkoxylates and branched ethylene oxide / propylene oxide block copolymers as dispersants for aqueous pesticidal suspensions.
  • the prior art particularly recommends ethylenediamine-ethylene oxide / propylene oxide block copolymers as wetting agents for disperseone paints.
  • a disadvantage of the ethylene diamine-ethylene oxide / propylene oxide block copolymers is the dark color and the ammoniacal odor.
  • the compounds of the formula (I) enhance the color intensity of emulsion paints tinted with organic colored pigments and carbon black pigments and prevent rubout.
  • the compounds of formula (I) improve the wetting power of the emulsion paint without affecting the rheological properties of the emulsion paint and they defoamer and deaerate in the production of the paint.
  • the object of the present invention was therefore to find suitable compounds which are added to the emulsion paints in order to avoid the described rubout problems and which show no negative side effects.
  • Another object of the invention is the use of compounds of formula (I) as deaerating wetting and dispersing agent in the above-mentioned emulsion paints.
  • Another object of the invention is a process for venting the above-mentioned emulsion paints by the emulsion paints at least one compound of formula (I) is added.
  • the rubout will be after the in US 3840383 determined test determined.
  • the abovementioned monomers for preparing the polymer dispersion with further comonomers preferably olefins or Hällogen faced olefins having 2 to 8 carbon atoms such.
  • comonomers preferably olefins or Hällogen faced olefins having 2 to 8 carbon atoms such.
  • Suitable components (B) are inorganic white pigments and fillers such as, for example, titanium dioxides, calcium carbonates, talc, kaolin, barium sulfates, zinc sulfides, zinc oxides. Preference is also given to using mixtures of said inorganic white pigments.
  • a particularly preferred mixture of inorganic white pigments contains titanium dioxide, calcium carbonate, talc and kaolin.
  • component (C) are monoazo, disazo, laked azo, ⁇ -naphthol, naphthol AS, benzimidazolone, disazo condensation, azo metal complex pigments and polycyclic pigments such. Phthalocyanine, quinacridone, Perylene, perinone, thioindigo, anthanthrone, anthraquinone, flavanthrone, indanthrone, isoviolanthrone, pyranthrone, dioxazine, quinophthalone, isoindolinone, isoindoline and diketopyrrolopyrrole pigments or carbon blacks.
  • organic colored pigments are carbon black pigments, such as. B. gas or Furnaceruße; Monoazo and disazo pigments, in particular the Color Index Pigments Pigment Yellow 1, Pigment Yellow 3, Pigment Yellow 12, Pigment Yellow 13, Pigment Yellow 14, Pigment Yellow 16, Pigment Yellow 17, Pigment Yellow 73, Pigment Yellow 74, Pigment Yellow 81, Pigment Yellow® 83, Pigment Yellow® 87, Pigment Yellow® 97, Pigment Yellow® 111, Pigment Yellow® 126, Pigment Yellow® 127, Pigment Yellow® 128, Pigment Yellow® 155, Pigment Yellow® 174, Pigment Yellow® 176, Pigment Yellow® 191, Pigment Yellow® 213, Pigment Yellow 214, Pigment Red 219, Pigment Red 38, Pigment Red 144, Pigment Red 214, Pigment Red 242, Pigment Red 262, Pigment Red 266, Pigment Red 269, Pigment Red 274, Pigment Orange 13, Pigment Orange 34 or Pigment Brown 41; ⁇ -Naphthol and Naph
  • Component (D) is a branched alkoxylation product of polyhydric alcohols or alkanolamines.
  • A represents a group derived from a polyhydric alcohol or an alkanolamine.
  • the term "derived” is understood to mean the formal abstraction of the hydrogen atoms capable of alkoxylation.
  • Preferred polyhydric alcohols from which A is derived are glycerin, butanetriol, hexanetriol, trimethylolpropane, pentaerythtritol, xylithol, sugar alcohols (alditols) such as mannitol, isomalt, lactitol, sorbitol, glucitol, xylitol, theirtol and erythritol.
  • polyhydric alcohols have as many alkoxylation-capable hydrogen atoms as they comprise OH groups.
  • A is derived from alkanolamines such as ethanolamine, diethanolamine and triethanolamine.
  • alkanolamines have as many hydrogen atoms capable of alkoxylation as they comprise OH groups and NH groups and twice as many hydrogen atoms capable of alkoxylation as they comprise NH 2 groups.
  • the hydrogen atoms capable of alkoxylation are also referred to herein as active hydrogen atoms.
  • A preferably comprises up to 8 active hydrogen atoms, in particular 4 to 6 active hydrogen atoms.
  • x is preferably equal to the number of active hydrogen atoms in A. In another preferred embodiment, x is 3, 4, 5 or 6.
  • the components (E) are customary auxiliaries used for emulsion paints, such as wetting agents, dispersants, defoamers, rheology additives, biocides, fungicides, algicides, buffer substances, such as sodium hydroxide solution, ammonia solution, amines, such as 2-amino-2-methyl-1-propanol, acids, such as sulfuric acid. Hydrochloric acid and acetic acid.
  • Suitable wetting and dispersing agents are nonionic surfactants from the class of alkylpolyethylene glycol ethers, fatty acid ethoxylates, alkylpolyglycosides, sorbitan ester ethoxylates, alkynediol ethoxylates, ethylene oxide and propylene oxide block copolymers and addition products of ethylene oxide and propylene oxide with alcohols, methyl, butyl and benzyl end-capped alcohol ethoxylates and alkylphenol ethoxylates.
  • Suitable dispersants for inorganic pigments and fillers are homo- and copolymers of acrylic acid, methacrylic acid, maleic acid, fumaric acid and acrylic acid. and methacrylic acid esters and their sodium, potassium and ammonium salts.
  • Suitable defoamers are mineral oil defoamers, silicone defoamers or defoamers based on polyalkylene glycol ethers.
  • Defoaming components of said defoamer classes are hydrophobic solid particles such as hydrophobically modified silica, fatty acid salts of di- and trivalent cations such as aluminum stearate and calcium stearate, amide waxes such as ethylenebisstearylamide and silicone resins.
  • Typical rheology additives are bentonites, silica, cellulose ethers, hydrophobically modified urethanes and alkali-soluble acrylate thickeners.
  • the emulsion paints of the invention usually contain preservatives to prevent infestation with microorganisms.
  • Typical preservatives are formaldehyde and formaldehyde-releasing compounds such as dihydroxy-2,5-dioxahexane, chloromethylisothiazolinone, benzylisothiazolinone, benzimidazolinone and bronopol.
  • film preservatives can be added to the emulsion paints.
  • diuron, carbendazim, octylisothiazolinone, dichloroctylisothiazolinone, zinc pyrithione, terbutryn and irgarol are useful as film preservatives.
  • film-forming agents substances are used which lower the minimum film-forming temperature to below 5 ° C., such as, for example, white spirit, methylpropylene glycol, methyldipropylene glycol, methyltripropylene glycol, butylglycol, butyldiglycol, butyldipropylene glycol and butyltripropylene glycol, diethyleriglycolzoate, trimethylpentane-1,3-diol monoisobutyrate, isodecylbenzoate, isononylbenzoate, Monoethylene glycol and monopropylene glycol monooleate and lactic acid esters of alcohols having 6 to 30 carbon atoms.
  • white spirit methylpropylene glycol, methyldipropylene glycol, methyltripropylene glycol, butylglycol, butyldiglycol, butyldipropylene glycol and butyltripropylene glycol, diethyleriglycolzoate
  • acids and alkalis such as sodium hydroxide solution, ammonia solution, amines such as 2-amino-2-methyl-1-propanol, triethanolamine, dimethylaminoethanol and acids such as sulfuric acid, hydrochloric acid, acetic acid and formic acid are used for the dispersion paints according to the invention.
  • further components (F) can be added to the dispersion paint according to the invention.
  • inorganic colored pigments can also be added to emulsion paints in order to set a desired color shade with a mixture of organic and inorganic pigments.
  • Suitable inorganic colored pigments are iron oxides, magnetites, manganese iron oxides, chromium oxides, ultramarine, nickel or chromium antimony titanium oxides, marigantite rutile, cobalt oxides, mixed oxides of cobalt and aluminum, rutile mixed phase pigments, rare earth sulfides, spinels of cobalt with nickel and zinc, spinels based on iron and chromium with copper, zinc and manganese, bismuth vanadate and extender pigments.
  • the emulsion paints according to the invention can moreover develop further film-forming components, such as silicone resins, potassium silicate or alkyd resin dispersions.
  • the emulsion paints according to the invention preferably contain 1 to 75% by weight of (A), in particular 5 to 50% by weight of (A), preferably 1 to 70% by weight of (B), in particular 2 to 50% by weight (B ), preferably 0.1 to 10 wt .-% (C), in particular 0.2 to 5 wt .-% (C), preferably 0.05 to 2 wt .-% (D), in particular 0.1 to 0 , 5 wt .-% (D), preferably 0.01 to 10 wt .-% (E), in particular 0.1 to 2 wt .-% (E) and preferably 1 to 70 wt .-% (F), in particular 2 to 50 wt .-% (F).
  • the emulsion paints of the invention preferably contain water in an amount of at least 20% by weight, in particular from 20 to 80% by weight, especially ad 100% by weight.
  • the emulsion paints of the invention are prepared in a conventional manner by first dispersing the white pigments and fillers and then metering in the polymer dispersion. The produced white dispersion paint is then tinted with one or more pigment preparations to the desired shade.
  • Table 1 formulation for white dispersion paints No. component Composition / property in% by weight 1 water 18.1 2 Tylose ® MH 10000 YP2 Cellulose ethers, thickeners 0.2 3 Mowiplus ® XW 330 Dispersant for inorganic pigments 0.3 4 wetting agent See Table 2 0.3 5 D-Foam-R C 113 Mineral oil 0.2 6 Titanium dioxide Kronos® 2160 Titanium dioxide, white pigment 20.0 7 Omyacarb ® 5 GU Calcium carbonate, filler 20.0 8th Ammonia solution (25%) alkalization 0.2 9 Mowilith ® LDM 7717 (about 50%) Acrylate dispersion, binder 40.0 10 Tafigel ® PUR 40 1: 9 in water urethane thickeners 0.4 11 Nipacide ® BIT 10 W Benzisothiazolinone, biocide 0.2 total 100
  • the components 1 - 5 are presented and then dispersed with a dissolver disk with the components 6 and 7 to a pigment dispersion at high stirrer speeds (labordissolver at 3000 rev / min). Subsequently, components 8-11 are added with slower stirring, since the binders used can be difficult to attack (laboratory dissolvers at 500 rpm).
  • wetting agents of the emulsion paints according to the invention and comparative examples example wetting agent product 1 (V) Alcohol ethoxylate with 7 moles of ethyl dioxide Emulsogen® LCN 070 2 (V) Ethylene oxide / propylene oxide block copolymer having an EO-PO-EO block structure and 10% ethylene oxide, linear Genapol ® PF 10 3 (V) Ethylene oxide / propylene oxide block copolymer having an EO-PO-EO block structure and 20% ethylene oxide, linear Genapol ® PF 20 4 (V) Ethylene oxide / propylene oxide block copolymer having an EO-PO-EO block structure and 40% ethylene oxide, linear Genapol ® PF 40 5 (V) Ethylenediamine ethylene oxide / propylene oxide block copolymer Genapol ® PN 30 6 (V) Alcohol alkoxylate with 8 moles of ethylene oxide and 4 mole
  • the wetting agents according to Example 8, 9 and 10 are block alkoxylates.
  • the surface-active substances of the white dispersion paints may tend to foam, which may hinder and prolong the production process. Due to the relatively high viscosity of the white dispersion paints, the foam is trapped in the emulsion paint so that it can no longer escape. Defoamers are used to prevent foaming, the concentration of which depends on the foaming tendency of the surface-active compounds. It is therefore advantageous if the wetting and dispersing agents used are weakly foaming substances or even defoaming. Of the emulsion paints produced, therefore, the density is determined with a pycnometer from Elcometer Ltd, Manchester. The higher the density of the emulsion paint, the lower the air entrapment.
  • rheology additives are added to the dispersion paints according to the invention, for example cellulose ethers, urethane thickeners and acrylate thickeners.
  • wetting agents especially with urethane thickeners, so that the viscosity can be lowered with the addition of wetting agents. It is therefore advantageous if the wetting agents used do not lower the viscosity of the emulsion paint.
  • the viscosity of the white dispersion paint is determined after one day with a Brookfield viscometer, spindle # 4 at 100 rpm. The viscosity of the white dispersion paint should not change significantly after addition of the wetting agent.
  • the surface tension is measured.
  • the white dispersion paint is diluted with water in a weight ratio of 1: 1 and the surface tension is determined using a Lauda Tensiometer, which works according to the platinum ring method according to ASTM D971.
  • the effectiveness of the wetting agents used is reflected in a lowering of the surface tension. The lower the surface tension of the diluted white dispersion paints, the more effective is the net effect of the products used.
  • tinting pastes are added to the white dispersion paints.
  • 200 g of tinted emulsion paint consisting of 98 wt .-% white dispersion paint and 2 wt .-% of a blue pigment paste in a tin can and homogenized for 60 seconds in an Inkshaker 500 from. Olbrich Know How, Hemer ,
  • the blue pigment paste used has the following composition. Table 3: Composition of the blue pigment paste for tinting the emulsion paints No.
  • the tinted emulsion paints are coated after one day on a test board with a 120 .mu.m knife on a film applicator, model 509 MC Fa. Erichsen GmbH, Hemer. After 7 minutes, the rubout test on the drying Falbfilm in the font US 3840383 described manner performed. From the fully dried film, the colorimetric values are determined after 24 hours with a Konica - Minolta Model CM 3600 spectrophotometer.
  • Example 5 The emulsion paints according to the invention of Examples 8 to 10 together with Example 5 (V) show the best results with respect to the prior art:
  • the wetting agent from Example 1 (V) has a marked tendency to foam, resulting in a lower density of approximately 1.33 g / ml and higher air entrapment than the wetting agents of Examples 8-10.
  • the wetting agents of Examples 2 (V) and 6 (V) show a lower net effect and a higher surface tension of about 36 mN / m over the wetting agents in Examples 8 to 10.
  • Example 5 shows comparable results to the wetting agents of Examples 8 to 10, but in contrast to these has an ammoniacal odor and a dark color while the wetting agents of Examples 8-10 are free of ammoniacal odor and show a light to clear color.
  • the dark color of the wetting agent in Example 5 (V) is caused by using ethylenediamine as the starting alkoxylation molecule.
  • the wetting agents of Examples 8 to 10 are colorless to yellowish and are free of ammoniacal odor.
  • the wetting agent in Example 7 (V) is wholly unsuitable because, similar to Example 1 (V), the tinting strength lags far behind the tints of Examples 8-10.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Wood Science & Technology (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)

Description

Gegenstand der vorliegenden Erfindung sind wässrige Dispersionsfarben, die verzweigte Polyalkylenglykolether als entlüftende Netz- und Dispergiermittel enthalten, sowie die Verwendung der verzweigten Polyalkylenglykolether als entlüftende Netz- und Dispergiermittel für wässrige Dispersionsfarben.The present invention relates to aqueous emulsion paints which contain branched polyalkylene glycol ethers as deaerating wetting agents and dispersants, and to the use of the branched polyalkylene glycol ethers as deaerating wetting and dispersing agents for aqueous emulsion paints.

Wässrige Dispersionsfarben enthalten Polymerdispersionen, auch Bindemittel, Latex oder Polymeremulsionen genannt, anorganische Weißpigmente und Füllstoffe, sowie Hilfsmittel wie Netz- und Dispergiermittel, Rheologieadditive, Entschäumer, Konservierungsmittel, Fungizide, Algizide, Filmbildehilfsmittel, Lösemittel und Puffersubstanzen. Beim Abtönen wässriger Dispersionsfarben werden Pigmentpräparationen volumetrisch oder gravimetrisch zudosiert und in der Dispersionsfarbe homogen verteilt. Das Verteilen kann von Hand durch Rühren erfolgen oder mittels einer elektrischen Rührers oder in einem Farbmischgerät, z. B. einer Schüttelmaschine oder auf einem Rütteltisch, auch Inkshaker oder Paintshaker genannt.Aqueous emulsion paints contain polymer dispersions, also called binders, latex or polymer emulsions, inorganic white pigments and fillers, as well as auxiliaries such as wetting and dispersing agents, rheology additives, defoamers, preservatives, fungicides, algicides, film-forming aids, solvents and buffer substances. When tinting aqueous emulsion paints, pigment preparations are metered in volumetrically or gravimetrically and distributed homogeneously in the emulsion paint. The spreading can be done by hand by stirring or by means of an electric stirrer or in a paint mixer, z. As a shaker or on a vibrating table, also called Inkshaker or Paintshaker.

Beim Abtönen mit Pigmentpräparationen, die organische Pigmente oder Rüßpigmente enthalten, kommt es oft zu Streifigkeit und zu einem unruhigen Farbbild aufgrund von Farbtonunterschieden. Die organischen Pigmente flokkulieren in der Farbe und während des Trocknungsprozesses, so dass die Farbstärke reduziert wird. Beim Streichen oder Rollen werden die Pigmentagglomerate wieder aufgetrennt, aber unterschiedlich stark, so dass es zu den beobachteten Farbtonunterschieden kommt. Im Labor wird dieses Phänomen im Rubout-Test simuliert. Der Rubout-Test wird in der Schrift US-3840383 beschrieben.Tinting with pigment preparations containing organic pigments or red pigments often results in streakiness and a disturbed color image due to hue differences. The organic pigments flocculate in the paint and during the drying process, so that the color strength is reduced. When brushing or rolling the pigment agglomerates are separated again, but different degrees, so that it comes to the observed hue differences. In the laboratory this phenomenon is simulated in the rubout test. The rubout test is in the font US 3840383 described.

Zum Vermeiden der Farbtonunterschiede und von Rubout werden den Dispersionsfarben geeignete Netzmittel zugesetzt.To avoid the color differences and rubout, suitable wetting agents are added to the dispersion paints.

US-2006/207476 beschreibt Latex-kompatible Tenside ausgewählt aus der US 2006/207476 describes latex-compatible surfactants selected from the

Gruppe der Nonylphenoletherphoshorsäureester, Nonylphenolethoxylate, Alkylpolyethylenglykolether, Dinonylsulfosuccinat, difunktionale Propylenoxid/Ethlyenoxid-Blockpolymere (mit sekundären OH-Gruppen), sekundäre Alkoholethoxylate und u. a. hydriertes Rizinusölethoxylat mit 40 Mol Ethylenoxid und Dispergiermittel für universale Farbkasten, die als Abtönpasten sowohl für wässrige Dispersionsfarben als auch für lösemittelhaltige Alkydlacke eingesetzt werden können.Nonylphenol ether phosphate esters, nonylphenol ethoxylates, alkyl polyethylene glycol ethers, dinonylsulfosuccinate, difunctional propylene oxide / ethylene oxide block polymers (having secondary OH groups), secondary alcohol ethoxylates, and the like. a. Hydrogenated castor oil ethoxylate with 40 moles of ethylene oxide and dispersing agent for universal ink fountain, which can be used as tinting pastes for aqueous emulsion paints as well as for solvent-based alkyd coatings.

US-2008/110368 beschreibt eine Farbenformulierung aus einem Pigmentpulver und nichtionischen Tensiden ausgewählt aus der Gruppe der Acetylentenside, Alkylphenolethoxylate, Ethylenoxid/Propylenoxid-Blockcopolymere, Alkoholethoxylate und deren Mischungen. US 2008/110368 describes a paint formulation of a pigment powder and nonionic surfactants selected from the group of acetylene surfactants, alkylphenol ethoxylates, ethylene oxide / propylene oxide block copolymers, alcohol ethoxylates and mixtures thereof.

Obwohl nach dem Stand der Technik eine Vielzahl von Verbindungen als geeignetes Netz- und Dispergiermittel vorgeschlagen werden, kommt es in der Praxis immer wieder zu Problemen mit Rubout nach dem Abtönen von Dispersionsfarben mit organischen Pigmentpräparationen.Although a variety of compounds are proposed as a suitable wetting and dispersing agent in the prior art, there are always problems in practice with rubout after tinting of emulsion paints with organic pigment preparations.

Alkoxylate werden in der Literatur bereits für eine Vielzahl von Anwendungen und in unterschiedlichen chemischen Zusammensetzungen beschrieben. Die Hauptzahl der beschriebenen Alkoxylate sind lineare Alkoholalkoxylate oder lineare Ethylenoxid/Propylenoxid-Blockcopolymere.Alkoxylates are already described in the literature for a variety of applications and in different chemical compositions. The majority of the alkoxylates described are linear alcohol alkoxylates or linear ethylene oxide / propylene oxide block copolymers.

DE-A-10332527 beschreibt die Verwendung von Polyalkylenoxiden zur Vermeidung der Eindickung von mit Schutzkolloiden stabilisierten, wässrigen Polymerdispersionen. DE-A-10332527 describes the use of polyalkylene oxides to prevent the thickening of protective colloid-stabilized, aqueous polymer dispersions.

EP-A-0115926 beschreibt die Verwendung von wasserlöslichen Polyoxypropylen/Polyoxyethylen/Polyoxypropylen-Blockcopolymere in wässrigen Metallbearbeitungskühlschmierstoffen. EP-A-0115926 describes the use of water-soluble polyoxypropylene / polyoxyethylene / polyoxypropylene block copolymers in aqueous metalworking coolants.

EP-A-1167452 beschreibt die Verwendung von blockcopolymeren Phosphorsäureestern und deren Salzen als Pigmentnetzmittel für Pigmentpasten, wässrige, lösemittelhaltige, lösemittelarme und lösemittelfreie Lacke und Druckfarben. Die blockcopolymeren Phosphorsäureester werden durch blockweises Umsetzen von Alkylol mit Styroloxid, Ethylenoxid und optional mit weiteren Alkylenoxiden hergestellt und anschließend zum Phosphorsäureester umgesetzt. EP-A-1167452 describes the use of block copolymeric phosphoric acid esters and their salts as pigment wetting agents for pigment pastes, aqueous, solvent-based, low-solvent and solvent-free paints and printing inks. The block copolymers of phosphoric acid are prepared by blockwise reaction of alkylol with styrene oxide, ethylene oxide and optionally with other alkylene oxides and then reacted to the phosphoric acid ester.

EP-A-1771520 beschreibt Alkoholalkoxylate als schaumarme Netzmittel für Beschichtungsstoffe aus Bindemitteln, Pigmenten, Füllstoffen, Additiven und Lösemitteln. EP-A-1771520 describes alcohol alkoxylates as low-foaming wetting agents for coating materials consisting of binders, pigments, fillers, additives and solvents.

US-3945964 beschreibt Alkoholalkoxylate als Dispergiermittel für wässrige Epoxydharzdispersionen. US 3945964 describes alcohol alkoxylates as dispersants for aqueous epoxy resin dispersions.

US-4091164 beschreibt Ethylenoxid/Propylenoxid-Blockcopolymere als Dispergiermittel für anorganische Pigmente und Füllstoffe in thermoplastischen Kunststoffen. US 4091164 describes ethylene oxide / propylene oxide block copolymers as dispersants for inorganic pigments and fillers in thermoplastics.

US-5114607 beschreibt Ethylenoxid/Propylenoxid-Blockcopolymere als schwachschäumende Tenside in flüssigen Metallreinigern. US 5114607 describes ethylene oxide / propylene oxide block copolymers as low-foaming surfactants in liquid metal cleaners.

US-5500219 beschreibt Ethylenoxid/Propylenoxid-Blockcopolymere als Dispergiermittel für in Wasser dispergierbare Pestizidgranulate. US 5500219 describes ethylene oxide / propylene oxide block copolymers as dispersants for water-dispersible pesticide granules.

US-6083998 beschreibt Ethylenoxid/Propylenoxid-Blockcopolymere als Entschäumerkomponente für Fermentationsprozesse. US 6083998 describes ethylene oxide / propylene oxide block copolymers as defoamer component for fermentation processes.

US-A-2003/144397 beschreibt Alkoholalkoxylate als Emulgatoren für wässrige Alkyldharzfarben. US-A-2003/144397 describes alcohol alkoxylates as emulsifiers for aqueous Alkyldharzfarben.

US-A-2004/254295 beschreibt Alkoholalkoxylate als Emulgatoren für Emulsionspolymere. US-A-2004/254295 describes alcohol alkoxylates as emulsifiers for emulsion polymers.

US-A-2005/288389 beschreibt Ethylenoxid/Propylenoxid-Blockcopolymere als Netzmittel für hydrophoben Schmutz. US-A-2005/288389 describes ethylene oxide / propylene oxide block copolymers as wetting agents for hydrophobic soil.

WO-02/16471 beschreibt Alkoholalkoxylate als Dispergiermittel für organische Pigment in lösemittelhaltigen Lacken. WO-02/16471 describes alcohol alkoxylates as a dispersant for organic pigment in solvent-based paints.

Auch verzweigte Alkoxylate und Pfropfpolymere mit Ethylenoxid/Propylenoxid-Seitenketten werden in der Literatur als Netz- und Dispergiermittel beschrieben.Branched alkoxylates and graft polymers with ethylene oxide / propylene oxide side chains are also described in the literature as wetting and dispersing agents.

EP-A-1643833 beschreibt Alkanolalkoxylate als Penetrationsförderer sowie ein Ethylendiaminalkoxylat-Derivat als Emulsionsstabilisator oder als Kristallisationsinhibitor in Pflanzenschutzformulierungen. EP-A-1643833 describes alkanol alkoxylates as penetration promoters and an ethylenediamine alkoxylate derivative as an emulsion stabilizer or as a crystallization inhibitor in crop protection formulations.

EP-A-1650246 beschreibt alkoxylierte Epoxyd-Amin-Addukte mit einem zahlenmittleren Molekulargewicht von mehr als 500 g/mol, die herstellbar sind durch die Umsetzung von Mono- und Polyepoxyden, primären oder sekundären Aminen und Alkanolaminen und Alkylenoxiden als Netz- und Dispergiermittel für organische und anorganische Pigmente und Füllstoffe in Pigmentpräparationen. In derselben Schrift werden auch basische Polyalkylenoxide auf Basis von alkoxyliertem Ethylendiamin als Netz- und Dispergiermittel als Stand der Technik beschrieben. EP-A-1650246 describes alkoxylated epoxy-amine adducts having a number average molecular weight of more than 500 g / mol, which can be prepared by the reaction of mono- and polyepoxides, primary or secondary amines and alkanolamines and alkylene oxides as wetting and dispersing agents for organic and inorganic pigments and Fillers in pigment preparations. The same document also describes basic polyalkylene oxides based on alkoxylated ethylenediamine as wetting and dispersing agent as prior art.

US-4540442 beschreibt Ethylendiamin-Ethylenoxid/Propylenoxid-Blockcopolymer als Reinigungskomponente für wässrige Lackentfernungsbeizen. US 4540442 describes ethylenediamine-ethylene oxide / propylene oxide block copolymer as a cleaning component for aqueous paint removal stains.

US-5629260 beschreibt die Verwendung von verzweigten Ethylenoxid/Propylenoxid-Blockcopolymere als Netzmittel für wässrige Herbizidlösungen. US 5629260 describes the use of branched ethylene oxide / propylene oxide block copolymers as wetting agents for aqueous herbicide solutions.

US-6028046 beschreibt alkoxylierte Polyimine als Vergrauungsinhibitoren für Textilwaschmittel. US 6028046 describes alkoxylated polyimines as graying inhibitors for textile detergents.

US-6300304 beschreibt alkoxylierte Polyimine als "Soil-Release"-Polymere in Waschmitteln. US 6300304 describes alkoxylated polyimines as "soil release" polymers in detergents.

US-A-2007/299228 beschreibt verzweigte Ethylenoxid/Propylenoxid-Blockcopolymere als Emulgatoren für wässrige Alkydharzdispersionen und wässrige Alkydharzfarben. US-A-2007/299228 describes branched ethylene oxide / propylene oxide block copolymers as emulsifiers for aqueous alkyd resin dispersions and aqueous alkyd resin paints.

WO-2007/124803 lehrt eine wässrige Pigmentpräparation, enthaltend (A) mindestens ein organisches und/oder anorganisches Pigment (B) Dispergiermittel und/oder Tenside, (C) einen drei- oder höherwertigen alkoxylierten Alkohol, (D) einen Polyglykolalkylether, (E) gegenüber hydrotrope Oligomere und/oder Polymere, (F) gegebenenfalls Fette, Öle oder Fettsäuren, (G) gegebenenfalls weitere zur Herstellung wässriger Pigmentdispersionen übliche Zusatzstoffe, und (H) Wasser, wobei als Komponente (C) Verbindungen der Formel (1) bevorzugt sind

Figure imgb0001
worin

R1, R2, R3
unabhängig voneinander Wasserstoff, ein verzweigter oder unverzweigter C1-C20-Alkyl- oder C3-C20-Cycloalkylrest, ein verzweigter oder unverzweigter C2-C20-Alkenyl- oder C3-C20-Cycloalkenylrest, ein Benzylrest oder ein Phenylrest ist, bevorzugt H, CH3 oder C2H5, und
m
durchschnittlich eine Zahl von 0 bis 100, vorzugsweise von 1 bis 60, besonders bevorzugt 4 bis 25 ist,
n
durchschnittlich eine Zahl von 0 bis 100, vorzugsweise von 0 bis 60, besonders bevorzugt 0 bis 10 ist,
p
durchschnittlich eine Zahl von 0 bis 100, vorzugsweise von 0 bis 60, besonders bevorzugt 0 bis 10 ist,
wobei die Summe m+n+p mindestens 1, bevorzugt mindestens 4 und besonders bevorzugt 15 bis 30, beträgt. WO-2007/124803 teaches an aqueous pigment preparation comprising (A) at least one organic and / or inorganic pigment (B) dispersants and / or surfactants, (C) a trihydric or higher alkoxylated alcohol, (D) a polyglycol alkyl ether, (E) versus hydrotrope oligomers and / or polymers, (F) optionally fats, oils or fatty acids, (G) optionally further customary for the preparation of aqueous pigment dispersions additives, and (H) water, wherein as component (C) compounds of formula (1) are preferred
Figure imgb0001
 wherein
R 1 , R 2 , R 3
independently of one another are hydrogen, a branched or unbranched C 1 -C 20 -alkyl or C 3 -C 20 -cycloalkyl radical, a branched or unbranched C 2 -C 20 -alkenyl or C 3 -C 20 -cycloalkenyl radical, a benzyl radical or Phenyl, preferably H, CH 3 or C 2 H 5 , and
m
average number is from 0 to 100, preferably from 1 to 60, particularly preferably 4 to 25,
n
average number is from 0 to 100, preferably from 0 to 60, particularly preferably 0 to 10,
p
average number is from 0 to 100, preferably from 0 to 60, particularly preferably 0 to 10,
where the sum m + n + p is at least 1, preferably at least 4 and particularly preferably 15 to 30.

WO-2009/130282 beschreibt die Verwendung von Alkoholalkoxylaten und verzweigten Ethylenoxid/Propylenoxid-Blockcopolymeren als Dispergiermittel für wässrige Pestizidsuspensionen. WO-2009/130282 describes the use of alcohol alkoxylates and branched ethylene oxide / propylene oxide block copolymers as dispersants for aqueous pesticidal suspensions.

Nach dem Stand der Technik werden besonders Ethylendiamin-Ethylenoxid/Propylenoxid-Blockcopolymere als Netzmittel für Disperisonsfarben empfohlen. Ein Ethylendiamin-Ethylenoxid/Propylenoxid-Blockcopolymer mit einem Trübungspunkt von 27 - 30 °C, gemessen mit 5 g in 25 cm3 25 % wässriger Butyldiglykol-Lösung, wird als Netzmitteln und Farbstärkeverbesserer für organische Pigmente und Ruße für wässrige Beschichtungsstöffe empfohlen. Nachteilig der Ethylendiamin-Ethylenoxid/Propylenoxid-Blockcopolymere ist die dunkle Farbe und der ammoniakalische Geruch.The prior art particularly recommends ethylenediamine-ethylene oxide / propylene oxide block copolymers as wetting agents for disperseone paints. An ethylene diamine-ethylene oxide / propylene oxide block copolymer having a cloud point of 27-30 ° C, as measured with 5 g in 25 cm 3 25% aqueous butyl diglycol solution, is recommended as wetting agents and color strength improvers for organic pigments and carbon blacks for aqueous coatings. A disadvantage of the ethylene diamine-ethylene oxide / propylene oxide block copolymers is the dark color and the ammoniacal odor.

Es wurde nun gefunden, dass die Verbindungen der Formel (I) die Farbstärke von mit organischen Buntpigmenten und Rußpigmenten abgetönten Dispersionsfarben verstärken und Rubout verhindern. Die Verbindungen der Formel (I) verbessern das Benetzungsvermögen der Dispersionsfarbe ohne einen Einfluss auf die rheologischen Eigenschaften der Dispersionsfarbe zu nehmen und sie wirken bei der Herstellung der Farbe entschäumend und entlüften.It has now been found that the compounds of the formula (I) enhance the color intensity of emulsion paints tinted with organic colored pigments and carbon black pigments and prevent rubout. The compounds of formula (I) improve the wetting power of the emulsion paint without affecting the rheological properties of the emulsion paint and they defoamer and deaerate in the production of the paint.

Aufgabe der vorliegenden Erfindung war es daher, geeignete Verbindungen zu finden, die den Dispersionsfarben zugesetzt werden, um die beschriebenen Rubout-Probleme zu vermeiden und die keine negativen Nebeneffekte zeigen.The object of the present invention was therefore to find suitable compounds which are added to the emulsion paints in order to avoid the described rubout problems and which show no negative side effects.

Überraschenderweise wurde gefunden, dass verzweigte Alkoxylate der Formel (I) diese Aufgabe erfüllen.Surprisingly, it has been found that branched alkoxylates of the formula (I) fulfill this task.

Gegenstand der Erfindung sind daher Dispersionsfarben, enthaltend Wasser und

  1. (A) mindestens eine Polymerdispersion, welche Homo- oder Copolymere von olefinisch ungesättigten Monomeren umfasst,
  2. (B) mindestens ein anorganisches Weißpigment oder ein anorganischer Füllstoff,
  3. (C) mindestens ein organisches Buntpigment oder Rußpigment,
  4. (D) mindestens eine Verbindung der Formel (I)
Figure imgb0002
 worin
A
ein aus einem mehrwertigen Alkohol oder Alkanolamin mit mindestens 3 aktiven Wasserstoffatomen abgeleiteter Rest,
R
ein Methyl oder Ethylrest,
R'
ein Wasserstoffatom oder ein Methyl-, Ethyl-, Propyl- oder Butylrest-,
n
eine ganze Zahl von 1 bis 250, vorzugsweise von 5 bis 100 und besonders bevorzugt von 10 bis 50,
m
eine ganze Zahl von 1 bis 500, vorzugsweise von 10 bis 200 und besonders bevorzugt von 20, bis 100,
x
kleiner oder gleich der Anzahl der aktiven Wasserstoffatome im mehrwertigen Alkohol oder Alkanolamin ist, von dem A abgeleitet ist,
und worin die Polyoxyethylen- und die Polyoxyalkylengruppen blockweise entsprechend der in der Formel I angegebenen Reihenfolge angeordnet sind.The invention therefore dispersion paints containing water and
  1. (A) at least one polymer dispersion which comprises homopolymers or copolymers of olefinically unsaturated monomers,
  2. (B) at least one inorganic white pigment or an inorganic filler,
  3. (C) at least one organic colored pigment or carbon black pigment,
  4. (D) at least one compound of the formula (I)
Figure imgb0002
 wherein
A
a radical derived from a polyhydric alcohol or alkanolamine having at least 3 active hydrogen atoms,
R
a methyl or ethyl radical,
R '
a hydrogen atom or a methyl, ethyl, propyl or butyl radical,
n
an integer from 1 to 250, preferably from 5 to 100, and more preferably from 10 to 50,
m
an integer from 1 to 500, preferably from 10 to 200, and more preferably from 20 to 100,
x
is less than or equal to the number of active hydrogens in the polyhydric alcohol or alkanolamine from which A is derived,
and wherein the polyoxyethylene and the polyoxyalkylene groups are arranged blockwise according to the order given in formula I.

Ein weiterer Gegenstand der Erfindung ist die Verwendung von Verbindungen der Formel (I) als entlüftendes Netz- und Dispergiermittel in den oben genannten Dispersionsfarben.Another object of the invention is the use of compounds of formula (I) as deaerating wetting and dispersing agent in the above-mentioned emulsion paints.

Ein weiterer Gegenstand der Erfindung ist ein Verfahren zur Entlüftung der oben genannten Dispersionsfarben indem den Dispersionsfarben mindestens eine Verbindung der Formel (I) zugesetzt wird.Another object of the invention is a process for venting the above-mentioned emulsion paints by the emulsion paints at least one compound of formula (I) is added.

Für die Zwecke dieser Erfindung wird der Rubout nach dem in US-3840383 beschriebenen Test bestimmt.For the purposes of this invention, the rubout will be after the in US 3840383 determined test determined.

In einer bevorzugten Ausführungsform enthalten die erfindungsgemäßen Dispersionsfarben zusätzlich

  • (E) übliche, für Dispersionsfarben verwendete Hilfsstoffe ausgewählt aus der Gruppe bestehend aus Netzmitteln, Dispergiermitteln, Entschäumern, Rheologieadditiven, Bioziden, Fungiziden, Algiziden, Filmbildehilfsmittel, Puffersubstanzen wie Natronlauge, Ammoniaklösung, Aminen wie 2-Amino-2-methyl-1-propanol, Säuren wie Schwefelsäure, Salzsäure und Essigsäure.
In a preferred embodiment, the emulsion paints according to the invention additionally contain
  • (E) customary auxiliaries used for emulsion paints selected from the group consisting of wetting agents, dispersants, defoamers, rheology additives, biocides, fungicides, algicides, film-forming agents, buffering agents such as sodium hydroxide, ammonia solution, amines such as 2-amino-2-methyl-1-propanol , Acids such as sulfuric acid, hydrochloric acid and acetic acid.

In einer weiteren bevorzugten Ausführungsform enthalten die erfindungsgemäßen Dispersionsfarben zusätzlich

  • (F) weitere Zusatzstoffe ausgewählt aus der Gruppe bestehend aus anorganischen Buntpigmenten, Silikonharzen, Kaliwasserglas oder Alkydharzdispersionen.
In a further preferred embodiment, the emulsion paints of the invention additionally contain
  • (F) further additives selected from the group consisting of inorganic colored pigments, silicone resins, potassium silicate or alkyd resin dispersions.

Als Komponente (A) eignen sich Polymerdispersionen auf Basis ungesättigter Monomere. Bevorzugte olefinisch ungesättigte Monomere sind beispielsweise

  • Vinylmonomere, wie Carbonsäureester des Vinylalkohols, beispielsweise Vinylacetat, Vinylpropionat, Vinylether der Isononansäure oder der Isodecansäure,
  • arylsubstituierte Olefine, wie Styrol und Stilben
  • olefinisch ungesättigte Carbonsäureester, wie Methylacrylat, Ethylacrylat, Propylacrylat, n-Butylacrylat, i-Butylacrylat, Pentylacrylat, Hexylacrylat, 2-Ethylhexylacrylat, Hydroxyethylacrylat sowie die entsprechenden Methacrylsäureester,
  • olefinisch ungesättigte Dicarbonsäureester, wie Dimethylmaleinat, Diethylmaleinat, Dipropylmaleinat, Dibutylmaleinat, Dipentylmaleinat, Dihexylmaleinat und Di-2-ethylhexylmaleinat,
  • olefinisch ungesättigte Carbonsäuren und Dicarbonsäuren, wie Acrylsäure, Methacrylsäure, Itaconsäure, Maleinsäure und Fumarsäure und ihre Natrium-, Kalium- und Ammoniumsalze,
  • olefinisch ungesättigte Sulfonsäuren und Phosphonsäuren und ihre Alkali-und Ammoniumsalze, wie Acrylamidomethylpropansulfonsäure und ihre Alkali- und Ammonium-, Alkylammonium und Hydroxyalkylammoniumsalze, Allylsulfonsäure und ihre Alkali- und Ammoniumsalze, Acryloyloxethylphosphonsäure und ihre Ammonium- und Alkalisalze sowie die entsprechenden Methacrylsäurederivate,
  • olefinisch ungesättigte Amine, Ammoniumsalze, Nitrile und Amide, wie Dimethylaminoethylacrylat, Acryloyloxethyltrimethylammoniumhalide, Acrylnitril, N-Methylacrylamid, N-Ethylacrylamid, N-Propylacrylamid, N-Methylolacrylamid sowie die entsprechenden Methacrylsäurederivate und Vinylmethylacetamid.
Suitable components (A) are polymer dispersions based on unsaturated monomers. Preferred olefinically unsaturated monomers are, for example
  • Vinyl monomers, such as carboxylic acid esters of vinyl alcohol, for example vinyl acetate, vinyl propionate, vinyl ethers of isononanoic acid or isodecanoic acid,
  • aryl-substituted olefins such as styrene and stilbene
  • olefinically unsaturated carboxylic acid esters, such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, i-butyl acrylate, pentyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate and the corresponding methacrylates,
  • olefinically unsaturated dicarboxylic acid esters, such as dimethyl maleate, Diethyl maleate, dipropyl maleate, dibutyl maleate, dipentyl maleate, dihexyl maleate and di-2-ethylhexyl maleate,
  • olefinically unsaturated carboxylic acids and dicarboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid and fumaric acid and their sodium, potassium and ammonium salts,
  • olefinically unsaturated sulfonic acids and phosphonic acids and their alkali metal and ammonium salts, such as acrylamidomethylpropanesulfonic acid and its alkali metal and ammonium, alkylammonium and hydroxyalkylammonium salts, allylsulfonic acid and its alkali metal and ammonium salts, acryloyloxethylphosphonic acid and its ammonium and alkali metal salts and the corresponding methacrylic acid derivatives,
  • olefinically unsaturated amines, ammonium salts, nitriles and amides, such as dimethylaminoethyl acrylate, acryloyloxethyltrimethylammonium halides, acrylonitrile, N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-methylolacrylamide and the corresponding methacrylic acid derivatives and vinylmethylacetamide.

In einer bevorzugten Ausführungsform werden die oben genannten Monomere zur Herstellung der Polymerdispersion mit weiteren Comonomeren, vorzugsweise Olefinen oder hälogenierten Olefinen mit 2 bis 8 Kohlenstoffatomen wie z. B. Ethylen, Propen, Buten, Pentan, 1,3-Butadien, Chloropren, Vinylchlorid, Vinylidenchlorid, Vinylidenfluorid und Tetrafluorethylen polymerisiert.In a preferred embodiment, the abovementioned monomers for preparing the polymer dispersion with further comonomers, preferably olefins or Hällogenierten olefins having 2 to 8 carbon atoms such. For example, ethylene, propene, butene, pentane, 1,3-butadiene, chloroprene, vinyl chloride, vinylidene chloride, vinylidene fluoride and tetrafluoroethylene polymerized.

Als Komponente (B) eignen sich anorganische Weißpigmente und Füllstoffe wie beispielsweise Titandioxide, Calciumcarbonate, Talkum, Kaolin, Bariumsulfate, Zinksulfide, Zinkoxide. Bevorzugt werden auch Mischungen der genannten anorganischen Weißpigmente verwendet. Eine besonders bevorzugte Mischung anorganischer Weißpigmente enthält Titandioxid, Calciumcarbonat, Talkum und Kaolin.Suitable components (B) are inorganic white pigments and fillers such as, for example, titanium dioxides, calcium carbonates, talc, kaolin, barium sulfates, zinc sulfides, zinc oxides. Preference is also given to using mixtures of said inorganic white pigments. A particularly preferred mixture of inorganic white pigments contains titanium dioxide, calcium carbonate, talc and kaolin.

Als Komponente (C) kommen Monoazo-, Disazo-, verlackte Azo-, β-Naphthol-, Naphthol AS-, Benzimidazolon-, Disazokondensations-, Azo-MetallkomplexPigmente und polycyclische Pigmente wie z. B. Phthalocyanin-, Chinacridon-, Perylen-, Perinon-, Thioindigo-, Anthanthron-, Anthrachinon-, Flavanthron-, Indanthron-, Isoviolanthron-, Pyranthron-, Dioxazin-, Chinophthalon-, Isoindolinon-, Isoindolin- und Diketopyrrolopyrrol-Pigmente oder Ruße in Betracht.As component (C) are monoazo, disazo, laked azo, β-naphthol, naphthol AS, benzimidazolone, disazo condensation, azo metal complex pigments and polycyclic pigments such. Phthalocyanine, quinacridone, Perylene, perinone, thioindigo, anthanthrone, anthraquinone, flavanthrone, indanthrone, isoviolanthrone, pyranthrone, dioxazine, quinophthalone, isoindolinone, isoindoline and diketopyrrolopyrrole pigments or carbon blacks.

Als beispielhafte Auswahl besonders bevorzugter organischer Buntpigmente sind dabei Rußpigmente, wie z. B. Gas- oder Furnaceruße; Monoazo- und Disazopigmente, insbesondere die Colour Index Pigmente Pigment Yellow 1, Pigment Yellow 3, Pigment Yellow 12, Pigment Yellow 13, Pigment Yellow 14, Pigment Yellow 16, Pigment Yellow 17, Pigment Yellow 73, Pigment Yellow 74, Pigment Yellow 81, Pigment Yellow 83, Pigment Yellow 87, Pigment Yellow 97, Pigment Yellow 111, Pigment Yellow 126, Pigment Yellow 127, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 174, Pigment Yellow 176, Pigment Yellow 191, Pigment Yellow 213, Pigment Yellow 214, Pigment Yellow 219, Pigment Red 38, Pigment Red 144, Pigment Red 214, Pigment Red 242, Pigment Red 262, Pigment Red 266, Pigment Red 269, Pigment Red 274, Pigment Orange 13, Pigment Orange 34 oder Pigment Brown 41; β-Näphthol- und Naphthol AS-Pigmente, insbesondere die Colour Index Pigmente Pigment Red 2, Pigment Red 3, Pigment Red 4, Pigment Red 5, Pigment Red 9, Pigment Red 12, Pigment Red 14, Pigment Red 53:1, Pigment Red 112, Pigment Red 146, Pigment Red 147, Pigment Red 170, Pigment Red 184, Pigment Red 187, Pigment Red 188, Pigment Red 210, Pigment Red 247, Pigment Red 253, Pigment Red 256, Pigment Orange 5, Pigment Orange 38 oder Pigment Brown 1; verlackte Azo- und Metallkomplexpigmente, insbesondere die Colour Index Pigmente Pigment Red 48:2, Pigment Red 48:3, Pigment Red 48:4, Pigment Red 57:1, Pigment Red 257, Pigment Orange 68 oder Pigment Orange 70; Benzimidazolinpigmente, insbesondere die Colour Index Pigmente Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 175, Pigment Yellow 180, Pigment Yellow 181, Pigment Yellow 194, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208, Pigment Violet 32, Pigment Orange 36, Pigment Orange 62, Pigment Orange 72 oder Pigment Brown 25; Isoindolinon- und Isoindolinpigmente, insbesondere die Colour Index Pigmente Pigment Yellow 139 oder Pigment Yellow 173; Phthalocyaninpigmente, insbesondere die Colour Index Pigmente Pigment Blue 15, Pigment Blue 15:1, Pigment Blue 15:2, Pigment Blue 15:3, Pigment Blue 15:4, Pigment Blue 15:6, Pigment Blue 16, Pigment Green 7 oder Pigment Green 36; Anthanthron-, Anthrachinon-, Chinacridon-, Dioxazin-, Indanthron-, Perylen-, Perinon- und Thioindigopigmente, insbesondere die Colour Index Pigmente Pigment Yellow 196, Pigment Red 122, Pigment Red 149, Pigment Red 168, Pigment Red 177, Pigment Red 179, Pigment Red 181, Pigment Red 207, Pigment Red 209, Pigment Red 263, Pigment Blue 60, Pigment Violet 19, Pigment Violet 23 oder Pigment Orange 43; Triarylcarboniumpigmente, insbesondere die Colour Index Pigmente Pigment Red 169, Pigment Blue 56 oder Pigment Blue 61; Diketopyrrolopyrrolpigmente, insbesondere die Colour Index Pigmente Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272, Pigment Orange 71, Pigment Orange 73, Pigment Orange 81 zu nennen.As an exemplary selection of particularly preferred organic colored pigments are carbon black pigments, such as. B. gas or Furnaceruße; Monoazo and disazo pigments, in particular the Color Index Pigments Pigment Yellow 1, Pigment Yellow 3, Pigment Yellow 12, Pigment Yellow 13, Pigment Yellow 14, Pigment Yellow 16, Pigment Yellow 17, Pigment Yellow 73, Pigment Yellow 74, Pigment Yellow 81, Pigment Yellow® 83, Pigment Yellow® 87, Pigment Yellow® 97, Pigment Yellow® 111, Pigment Yellow® 126, Pigment Yellow® 127, Pigment Yellow® 128, Pigment Yellow® 155, Pigment Yellow® 174, Pigment Yellow® 176, Pigment Yellow® 191, Pigment Yellow® 213, Pigment Yellow 214, Pigment Red 219, Pigment Red 38, Pigment Red 144, Pigment Red 214, Pigment Red 242, Pigment Red 262, Pigment Red 266, Pigment Red 269, Pigment Red 274, Pigment Orange 13, Pigment Orange 34 or Pigment Brown 41; β-Naphthol and Naphthol AS pigments, in particular the Color Index Pigments Pigment Red 2, Pigment Red 3, Pigment Red 4, Pigment Red 5, Pigment Red 9, Pigment Red 12, Pigment Red 14, Pigment Red 53: 1, Pigment Red Red 112, Pigment Red 146, Pigment Red 147, Pigment Red 170, Pigment Red 184, Pigment Red 187, Pigment Red 188, Pigment Red 210, Pigment Red 247, Pigment Red 253, Pigment Red 256, Pigment Orange 5, Pigment Orange 38 or Pigment Brown 1; laked azo and metal complex pigments, in particular the Color Index pigments Pigment Red 48: 2, Pigment Red 48: 3, Pigment Red 48: 4, Pigment Red 57: 1, Pigment Red 257, Pigment Orange 68 or Pigment Orange 70; Benzimidazoline pigments, in particular the Color Index pigments Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 175, Pigment Yellow 180, Pigment Yellow 181, Pigment Yellow 194, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208 , Pigment Violet 32, Pigment Orange 36, Pigment Orange 62, Pigment Orange 72 or Pigment Brown 25; Isoindolinone and isoindoline pigments, in particular the Color Index pigments Pigment Yellow 139 or Pigment Yellow 173; Phthalocyanine pigments, in particular the Color Index pigments Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6, Pigment Blue 16, Pigment Green 7 or Pigment Green 36; Anthanthrone, anthraquinone, quinacridone, dioxazine, indanthrone, perylene, perinone and thioindigo pigments, in particular the Color Index Pigments Pigment Yellow 196, Pigment Red 122, Pigment Red 149, Pigment Red 168, Pigment Red 177, Pigment Red 179, Pigment Red 181, Pigment Red 207, Pigment Red 209, Pigment Red 263, Pigment Blue 60, Pigment Violet 19, Pigment Violet 23 or Pigment Orange 43; Triarylcarboniumpigmente, in particular the Color Index pigments Pigment Red 169, Pigment Blue 56 or Pigment Blue 61; Diketopyrrolopyrrolpigmente, in particular the Color Index pigments Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272, Pigment Orange 71, Pigment Orange 73, Pigment Orange 81 to call.

Bei Komponente (D) handelt es sich um ein verzweigtes Alkoxylierungsprodukt mehrwertiger Alkohole oder Alkanolamine. In Formel (I) stellt A einen Rest dar, der aus einem mehrwertigen Alkohol oder einem Alkanolamin abgeleitet ist. Unter dem Begriff "abgeleitet" ist die formale Abstraktion der zur Alkoxylierung fähigen Wasserstoffatome zu verstehen. Bevorzugte mehrwertige Alkohole, von denen A sich ableitet, sind Glycerin, Butantriol, Hexantriol, Trimethylolpropan, Pentaerythtritol, Xylithol, Zuckeralkohole (Alditole) wie beispielsweise Mannitol, Isomalt, Lactitol, Sorbitol, Glucitol, Xylitol, Theirtol und Erythritol. Im Allgemeinen haben mehrwertige Alkohole so viele zur Alkoxylierung fähige Wasserstoffatome wie sie OH-Gruppen umfassen.Component (D) is a branched alkoxylation product of polyhydric alcohols or alkanolamines. In formula (I), A represents a group derived from a polyhydric alcohol or an alkanolamine. The term "derived" is understood to mean the formal abstraction of the hydrogen atoms capable of alkoxylation. Preferred polyhydric alcohols from which A is derived are glycerin, butanetriol, hexanetriol, trimethylolpropane, pentaerythtritol, xylithol, sugar alcohols (alditols) such as mannitol, isomalt, lactitol, sorbitol, glucitol, xylitol, theirtol and erythritol. In general, polyhydric alcohols have as many alkoxylation-capable hydrogen atoms as they comprise OH groups.

In einer weiteren bevorzugten Ausführungsform der Erfindung ist A aus Alkanolaminen wie Ethanolamin, Diethanolamin und Triethanolamin abgeleitet. Im Allgemeinen haben Alkanolamine so viele zur Alkoxylierung fähigen Wasserstoffatome wie sie OH-Gruppen und NH-Gruppen und zweimal so viele zur Alkoxylierung fähigen Wasserstoffatome wie sie NH2-Gruppen umfassen. Die zur Alkoxylierung befähigten Wasserstoffatome werden hier auch als aktive Wasserstoffatome bezeichnet.In a further preferred embodiment of the invention A is derived from alkanolamines such as ethanolamine, diethanolamine and triethanolamine. In general, alkanolamines have as many hydrogen atoms capable of alkoxylation as they comprise OH groups and NH groups and twice as many hydrogen atoms capable of alkoxylation as they comprise NH 2 groups. The hydrogen atoms capable of alkoxylation are also referred to herein as active hydrogen atoms.

A umfasst vorzugsweise bis zu 8 aktive Wasserstoffatome, insbesondere 4 bis 6 aktive Wasserstoffatome. x ist vorzugsweise gleich der Zahl der aktiven Wasserstoffatome in A. In einer weiteren bevorzugten Ausführungsform ist x gleich 3, 4, 5 oder 6.A preferably comprises up to 8 active hydrogen atoms, in particular 4 to 6 active hydrogen atoms. x is preferably equal to the number of active hydrogen atoms in A. In another preferred embodiment, x is 3, 4, 5 or 6.

Die Komponenten (E) sind übliche für Dispersionenfarben verwendete Hilfsstoffe wie Netzmittel, Dispergiermittel, Entschäumer, Rheologieadditive, Biozide, Fungizide, Algizide, Puffersubstanzen wie Natronlauge, Ammoniaklösung, Amine wie 2-Amino-2-methyl-1-propanol, Säuren wie Schwefelsäure, Salzsäure und Essigsäure.The components (E) are customary auxiliaries used for emulsion paints, such as wetting agents, dispersants, defoamers, rheology additives, biocides, fungicides, algicides, buffer substances, such as sodium hydroxide solution, ammonia solution, amines, such as 2-amino-2-methyl-1-propanol, acids, such as sulfuric acid. Hydrochloric acid and acetic acid.

Als Netz- und Dispergiermittel eignen sich nichtionische Tenside aus der Klasse der Alkylpolyethylenglykolether, Fettsäureethoxylate, Alkylpolyglykoside, Sorbitanesterethoxylate, Alkindiolethoxylate, Ethylenoxid und Propylenoxid-Blockcopolymere und Additionsprodukte von Ethylenoxid und Propylenoxid an Alkohole, Methyl-, Butyl- und Benzyl-endgruppenverschlossene Alkoholethoxylate und Alkylphenolethoxylayte. Weiterhin werden beispielsweise Netz- und Dispergiermittel aus der Klasse der anionischen Tenside aus der Gruppe der Natrium-, Kalium- und Ammoniumsalze von Fettsäuren, Natriumalkylbenzolsulfonate, Natriumalkylsulfonate, Natriumolefinsulfonate, Natriumpolynaphthalinsulfonate, Natriumdialkyldiphenyletherdisulfonate, Natrium-, Kalium- und Ammoniumalkylsulfate, Natrium-, Kalium- und Ammoniumalkylpolyethylenglykolethersulfate, Natrium-, Kalium- und Ammoniumalkylphenolpolyethylenglykolethersulfate, Natrium-, Kalium- und Ammoniummono- und dialkylsulfosuccinate und Monoalkylpolyoxethylsulfosuccinate, sowie Alkylpolyethylenglykoletherphosphorsäuremono-, di- und triester und deren Mischungen und Alkylphenolpolyethylenglykoletherphosphorsäuremono-, di- und triester und deren Mischungen, sowie deren Natrium-, Kalium- und Ammoniumsalze verwendet.Suitable wetting and dispersing agents are nonionic surfactants from the class of alkylpolyethylene glycol ethers, fatty acid ethoxylates, alkylpolyglycosides, sorbitan ester ethoxylates, alkynediol ethoxylates, ethylene oxide and propylene oxide block copolymers and addition products of ethylene oxide and propylene oxide with alcohols, methyl, butyl and benzyl end-capped alcohol ethoxylates and alkylphenol ethoxylates. Furthermore, wetting and dispersing agents from the class of anionic surfactants from the group of sodium, potassium and ammonium salts of fatty acids, sodium alkylbenzenesulfonates, sodium alkylsulfonates, sodium olefinsulfonates, sodium polynaphthalenesulfonates, sodium dialkyldiphenyl ether disulfonates, sodium, potassium and ammonium alkyl sulfates, sodium, potassium and Ammoniumalkylpolyethylenglykolethersulfate, sodium, potassium and Ammoniumalkylphenolpolyethylenglykolethersulfate, sodium, potassium and ammonium mono- and dialkylsulfosuccinate and Monoalkylpolyoxethylsulfosuccinate, and Alkylpolyethylenglykoletherphosphorsäuremono-, di- and triester and mixtures thereof and Alkylphenolpolyethylenglykoletherphosphorsäuremono-, di- and triesters and mixtures thereof, and their sodium , Potassium and ammonium salts used.

Als Dispergiermittel für anorganische Pigmente und Füllstoffe werden Homo- und Copolymere der Acrylsäure, Methacylsäure, Maleinsäure, Fumarsäure und Acryl- und Methacrylsäureester und deren Natrium-, Kalium- und Ammoniumsalze verwendet.Suitable dispersants for inorganic pigments and fillers are homo- and copolymers of acrylic acid, methacrylic acid, maleic acid, fumaric acid and acrylic acid. and methacrylic acid esters and their sodium, potassium and ammonium salts.

Als Entschäumer eignen sich Mineralölentschäumer, Siliconentschäumer oder Entschäumer auf Basis von Polyalkylenglykolethern. Entschäumende Komponenten der genannten Entschäumerklassen sind hydrophobe Feststoffteilchen wie hydrophobmodifizierte Silica, Fettsäuresalze zwei- und dreiwertiger Kationen wie Aluminiumstearat und Calciumstearat, Amidwachse wie Ethylenbisstearylamid und Siliconharze.Suitable defoamers are mineral oil defoamers, silicone defoamers or defoamers based on polyalkylene glycol ethers. Defoaming components of said defoamer classes are hydrophobic solid particles such as hydrophobically modified silica, fatty acid salts of di- and trivalent cations such as aluminum stearate and calcium stearate, amide waxes such as ethylenebisstearylamide and silicone resins.

Übliche Rheologieadditive sind Bentonite, Silica, Celluloseether, hydrophobmodifizerte Urethane und alkalilösliche Acrylatverdicker.Typical rheology additives are bentonites, silica, cellulose ethers, hydrophobically modified urethanes and alkali-soluble acrylate thickeners.

Die erfindungsgemäßen Dispersionsfarben enthalten üblicherweise Konservierungsmittel, um den Befall mit Mikroorganismen zu verhindern. Übliche Konservierungsstoffe sind Formaldehyd und Formaldehyd-abspaltende Verbindungen wie Dihydroxy-2,5-dioxahexan, Chlormethylisothiazolinon, Benzylisothiazolinon, Benzimidazolinon und Bronopol. Zur Verhinderung des Befalls mit Pilzen und Algen, insbesondere nach dem Aufbringen der Dispersionsfarben auf Außenwände, Fassaden, Dachsteine und Metall- und Kunststoffteile wie Regenrinnen im Außenbereich, können den Dispersionsfarben Filmkonservierungsmittel zugesetzt werden. Beispielsweise eignen sich Diuron, Carbendazim, Octylisothiazolinon, Dichloroctylisothiazolinon, Zinkpyrithion, Terbutryn und Irgarol als Filmkonservierungsmittel.The emulsion paints of the invention usually contain preservatives to prevent infestation with microorganisms. Typical preservatives are formaldehyde and formaldehyde-releasing compounds such as dihydroxy-2,5-dioxahexane, chloromethylisothiazolinone, benzylisothiazolinone, benzimidazolinone and bronopol. To prevent the infestation with fungi and algae, especially after the application of the emulsion paints on exterior walls, facades, roof tiles and metal and plastic parts such as gutters in the outdoor area, film preservatives can be added to the emulsion paints. For example, diuron, carbendazim, octylisothiazolinone, dichloroctylisothiazolinone, zinc pyrithione, terbutryn and irgarol are useful as film preservatives.

Als Filmbildehilfsmittel kommen Substanzen zum Einsatz, die die Mindestfilmbildetemperatur auf bis unter 5 °C herabsenken wie beispielsweise Testbenzin, Methylpropylenglykol, Methyldipropylenglykol, Methyltripropylenglykol, Butylglykol, Butyldiglykol, Butyldipropylenglykol und Butyltripropylenglykol, Diethyleriglykolbenzoat, Trimethylpentan-1,3-diol monoisobutyrat, Isodecylbenzoat, Isononylbenzoat, Monoethylenglykol und Monopropylenglykolmonooleat und Milchsäureester von Alkoholen mit 6 bis 30 Kohlenstoffatomen.As film-forming agents, substances are used which lower the minimum film-forming temperature to below 5 ° C., such as, for example, white spirit, methylpropylene glycol, methyldipropylene glycol, methyltripropylene glycol, butylglycol, butyldiglycol, butyldipropylene glycol and butyltripropylene glycol, diethyleriglycolzoate, trimethylpentane-1,3-diol monoisobutyrate, isodecylbenzoate, isononylbenzoate, Monoethylene glycol and monopropylene glycol monooleate and lactic acid esters of alcohols having 6 to 30 carbon atoms.

Als Puffersubstanzen werden für die erfindungsgemäßen Dispersionsfarben Säuren und Alkalien wie Natronlauge, Ammoniaklösung, Amine wie 2-Amino-2-methyl-1-propanol, Triethanolamin, Dimethylaminoethanol und Säuren wie Schwefelsäure, Salzsäure, Essigsäure und Ameisensäure verwendet.As buffer substances, acids and alkalis such as sodium hydroxide solution, ammonia solution, amines such as 2-amino-2-methyl-1-propanol, triethanolamine, dimethylaminoethanol and acids such as sulfuric acid, hydrochloric acid, acetic acid and formic acid are used for the dispersion paints according to the invention.

Der erfindungsgemäßen Dispersionsfarbe können gegebenenfalls weitere Komponenten (F) zugesetzt werden. Dispersionsfarben können gegebenenfalls auch anorganische Buntpigmente zugesetzt werden, um mit einer Mischung aus organischen und anorganischen Pigmenten einen gewünschten Farbton einzustellen.If appropriate, further components (F) can be added to the dispersion paint according to the invention. If desired, inorganic colored pigments can also be added to emulsion paints in order to set a desired color shade with a mixture of organic and inorganic pigments.

Geeignete anorganische Buntpigmente sind Eisenoxide, Magnetite, Manganeisenoxide, Chromoxide, Ultramarin, Nickel- oder Chromantimontitanoxide, Marigantitanrutile, Cobaltoxide, Mischoxide des Cobalts und Aluminiums, Rutilmischphasenpigmente, Sulfide der seltenen Erden, Spinelle des Cobalts mit Nickel und Zink, Spinelle basierend auf Eisen und Chrom mit Kupfer, Zink sowie Mangan, Bismutvanadat sowie Verschnittpigmente. Insbesondere werden die Colour Index Pigmente Pigment Yellow 184, Pigment Yellow 53, Pigment Yellow 42, Pigment Brown 24, Pigment Red 101, Pigment Blue 28, Pigment Blue 36, Pigment Green 50, Pigment Green 17, Pigment Black 11 und Pigment Black 33 verwendet.Suitable inorganic colored pigments are iron oxides, magnetites, manganese iron oxides, chromium oxides, ultramarine, nickel or chromium antimony titanium oxides, marigantite rutile, cobalt oxides, mixed oxides of cobalt and aluminum, rutile mixed phase pigments, rare earth sulfides, spinels of cobalt with nickel and zinc, spinels based on iron and chromium with copper, zinc and manganese, bismuth vanadate and extender pigments. In particular, the Color Index Pigments Pigment Yellow 184, Pigment Yellow 53, Pigment Yellow 42, Pigment Brown 24, Pigment Red 101, Pigment Blue 28, Pigment Blue 36, Pigment Green 50, Pigment Green 17, Pigment Black 11 and Pigment Black 33 are used ,

Die erfindungsgemäßen Dispersionsfarben können darüber hinaus weitere filmbildende Komponenten entfalten, wie Silikonharze, Kaliwasserglas oder Alkydharzdispersionen.The emulsion paints according to the invention can moreover develop further film-forming components, such as silicone resins, potassium silicate or alkyd resin dispersions.

Die erfindungsgemäßen Dispersionsfarben enthalten vorzugsweise 1 bis 75 Gew.-% (A), insbesondere 5 bis 50 Gew.-% (A), vorzugsweise 1 bis 70 Gew.-% (B), insbesondere 2 bis 50 Gew.-% (B), vorzugsweise 0,1 bis 10 Gew.-% (C), insbesondere 0,2 bis 5 Gew.-% (C), vorzugsweise 0,05 bis 2 Gew.-% (D), insbesondere 0,1 bis 0,5 Gew.-% (D), vorzugsweise 0,01 bis 10 Gew.-% (E), insbesondere 0,1 bis 2 Gew.-% (E) und vorzugsweise 1 bis 70 Gew.-% (F), insbesondere 2 bis 50 Gew.-% (F).The emulsion paints according to the invention preferably contain 1 to 75% by weight of (A), in particular 5 to 50% by weight of (A), preferably 1 to 70% by weight of (B), in particular 2 to 50% by weight (B ), preferably 0.1 to 10 wt .-% (C), in particular 0.2 to 5 wt .-% (C), preferably 0.05 to 2 wt .-% (D), in particular 0.1 to 0 , 5 wt .-% (D), preferably 0.01 to 10 wt .-% (E), in particular 0.1 to 2 wt .-% (E) and preferably 1 to 70 wt .-% (F), in particular 2 to 50 wt .-% (F).

Vorzugsweise enthalten die erfindungsgemäßen Dispersionsfarben Wasser in einer Menge von mindestens 20 Gew.-%, insbesondere 20 bis 80 Gew.-%, speziell ad 100 Gew.-%.The emulsion paints of the invention preferably contain water in an amount of at least 20% by weight, in particular from 20 to 80% by weight, especially ad 100% by weight.

BeispieleExamples

Die erfindungsgemäßen Dispersionsfarben werden auf übliche Weise hergestellt, indem zunächst die Weißpigmente und Füllstoffe dispergiert werden und anschließend die Polymerdispersion zudosiert wird. Die hergestellte Weißdispersionsfarbe wird anschließend mit einer oder mehreren Pigmentpräparationen auf den gewünschten Farbton abgetönt.The emulsion paints of the invention are prepared in a conventional manner by first dispersing the white pigments and fillers and then metering in the polymer dispersion. The produced white dispersion paint is then tinted with one or more pigment preparations to the desired shade.

Herstellen der WeißdispersionsfarbenMaking the white dispersion paints

Tabelle 1: Formulierung für WeißdispersionsfarbenTable 1: formulation for white dispersion paints Nr.No. Komponentecomponent Zusammensetzung/EigenschaftComposition / property in Gew.-%in% by weight 11 Wasserwater 18,118.1 22 Tylose® MH 10000 YP2Tylose ® MH 10000 YP2 Celluloseether, VerdickerCellulose ethers, thickeners 0,20.2 33 Mowiplus® XW 330Mowiplus ® XW 330 Dispergiermittel für anorganische PigmenteDispersant for inorganic pigments 0,30.3 44 Netzmittelwetting agent Siehe Tabelle 2See Table 2 0,30.3 55 D-Foam-R C 113D-Foam-R C 113 MineralölentschäumerMineral oil 0,20.2 66 Titandioxide Kronos® 2160Titanium dioxide Kronos® 2160 Titandioxid, WeißpigmentTitanium dioxide, white pigment 20,020.0 77 Omyacarb® 5 GUOmyacarb ® 5 GU Calciumcarbonat, FüllstoffCalcium carbonate, filler 20,020.0 88th Ammoniak-Lösung (25%ig)Ammonia solution (25%) Alkalisierungalkalization 0,20.2 99 Mowilith® LDM 7717 (ca. 50%ig)Mowilith ® LDM 7717 (about 50%) Acrylatdispersion, BindemittelAcrylate dispersion, binder 40,040.0 1010 Tafigel® PUR 40 1:9 in WasserTafigel ® PUR 40 1: 9 in water Urethanverdickerurethane thickeners 0,40.4 1111 Nipacide® BIT 10 WNipacide ® BIT 10 W Benzisothiazolinon, BiozidBenzisothiazolinone, biocide 0,20.2 Summetotal 100100

Zunächst werden die Komponenten 1 - 5 vorgelegt und anschließend mit einer Dissolverscheibe mit den Komponenten 6 und 7 zu einer Pigmentdispersion bei hohen Rührergeschwindigkeiten dispergiert (Labordissolver mit 3000 U/min). Anschließend werden die Komponenten 8 - 11 unter langsamerem Rühren zugegeben, da die verwendeten Bindemittel schweranfällig sein können (Labordissolver mit 500 U/min).First, the components 1 - 5 are presented and then dispersed with a dissolver disk with the components 6 and 7 to a pigment dispersion at high stirrer speeds (labordissolver at 3000 rev / min). Subsequently, components 8-11 are added with slower stirring, since the binders used can be difficult to attack (laboratory dissolvers at 500 rpm).

Als Netzmittel werden folgenden Substanzen verwendet. Tabelle 2: Netzmittel der erfindungsgemäßen Dispersionsfarben und Vergleichsbeispiele Beispiel Netzmittel Produkt 1 (V) Alkoholethoxylat mit 7 Mol Ethylerioxid Emulsogen® LCN 070 2 (V) Ethylenoxid/Propylenoxid Blockcopolymer mit einer EO-PO-EO Blockstruktur und 10% Ethylenoxid, linear Genapol® PF 10 3 (V) Ethylenoxid/Propylenoxid Blockcopolymer mit einer EO-PO-EO Blockstruktur und 20% Ethylenoxid, linear Genapol® PF 20 4 (V) Ethylenoxid/Propylenoxid Blockcopolymer mit einer EO-PO-EO Blockstruktur und 40% Ethylenoxid, linear Genapol® PF 40 5 (V) Ethylendiamin Ethylenoxid/Propylenoxid Blockcopolymerisat Genapol® PN 30 6 (V) Alkoholalkoxylat mit 8 Mol Ethylenoxid und 4 Mol Propylenoxid Genapol® EP 2584 7 (V) Alkoholethoxylat mit 8 Mol Ethylenoxid, endgruppenverschlossen mit Butylchlorid Genapol® BE 2410 8 Glyzerin + 24 EO + 48 PO 9 Butantriol + 24 EO + 48 PO 10 Hexantriol + 24 EO + 48 PO The following substances are used as wetting agents. Table 2: Wetting agents of the emulsion paints according to the invention and comparative examples example wetting agent product 1 (V) Alcohol ethoxylate with 7 moles of ethyl dioxide Emulsogen® LCN 070 2 (V) Ethylene oxide / propylene oxide block copolymer having an EO-PO-EO block structure and 10% ethylene oxide, linear Genapol ® PF 10 3 (V) Ethylene oxide / propylene oxide block copolymer having an EO-PO-EO block structure and 20% ethylene oxide, linear Genapol ® PF 20 4 (V) Ethylene oxide / propylene oxide block copolymer having an EO-PO-EO block structure and 40% ethylene oxide, linear Genapol ® PF 40 5 (V) Ethylenediamine ethylene oxide / propylene oxide block copolymer Genapol ® PN 30 6 (V) Alcohol alkoxylate with 8 moles of ethylene oxide and 4 moles of propylene oxide Genapol ® EP 2584 7 (V) Alcohol ethoxylate with 8 moles of ethylene oxide, end-capped with butyl chloride Genapol ® BE 2410 8th Glycerol + 24 EO + 48 PO 9 Butantriol + 24 EO + 48 PO 10 Hexane triol + 24 EO + 48 PO

Bei den Netzmitteln gemäß Beispiel 8, 9 und 10 handelt es sich um Blockalkoxylate.The wetting agents according to Example 8, 9 and 10 are block alkoxylates.

Luftgehalt der WeißdispersionsfarbenAir content of white dispersion paints

Die oberflächenaktiven Substanzen der Weißdispersionsfarben wie Netz- und Dispergiermittel und Emulgatoren der verwendeten Bindemittel können zum Schäumen neigen, was den Herstellprozess behindern und verlängern kann. Aufgrund der relativ hohen Viskosität der Weißdispersionsfarben wird der Schaum in der Dispersionsfarbe eingeschlossen, so dass er nicht mehr entweichen kann. Zur Vermeindung des Schäumaufbaus werden Entschäumer verwendet, deren Konzentration von der Schaumneigung der oberflächenaktiven Verbindungen abhängt. Vorteilhaft ist es daher, wenn die verwendeten Netz- und Dispergiermittel schwachschäumende Substanzen sind oder sogar entschäumend wirken. Von den hergestellten Dispersionsfarben wird daher mit einem Pyknometer der Firma Elcometer Ltd, Manchester die Dichte bestimmt. Je höher die Dichte der Dispersionsfarbe, des so niedriger ist der Lufteinschluss.The surface-active substances of the white dispersion paints, such as wetting and dispersing agents and emulsifiers of the binders used, may tend to foam, which may hinder and prolong the production process. Due to the relatively high viscosity of the white dispersion paints, the foam is trapped in the emulsion paint so that it can no longer escape. Defoamers are used to prevent foaming, the concentration of which depends on the foaming tendency of the surface-active compounds. It is therefore advantageous if the wetting and dispersing agents used are weakly foaming substances or even defoaming. Of the emulsion paints produced, therefore, the density is determined with a pycnometer from Elcometer Ltd, Manchester. The higher the density of the emulsion paint, the lower the air entrapment.

Viskosität der WeißdispersionsfarbenViscosity of the white dispersion paints

Für das Einstellen der rheologischen Eigenschaften werden den erfindungsgemäßen Dispersionsfarben Rheologieadditive zugesetzt, beispielsweise Celluloseether, Urethanverdicker und Acrylatverdicker. Zwischen den Rheologieadditiven und Netzmitteln kann zu einer Wechselwirkung kommen, insbesondere mit Urethanverdickern, so dass die Viskosität bei Zugabe der Netzmittel gesenkt werden kann. Vorteilhaft ist es daher, wenn die verwendeten Netzmittel die Viskosität der Dispersionsfarbe nicht senken. Die Viskosität der Weißdispersionsfarbe wird nach einem Tag mit einem Brookfield Viskosimeter, Spindel Nr. 4 bei 100 U/min bestimmt. Die Viskosität der Weißdispersionsfarbe soll sich nach Zugabe der Netzmittel nicht signifikant verändern.To adjust the rheological properties, rheology additives are added to the dispersion paints according to the invention, for example cellulose ethers, urethane thickeners and acrylate thickeners. There may be an interaction between the rheology additives and wetting agents especially with urethane thickeners, so that the viscosity can be lowered with the addition of wetting agents. It is therefore advantageous if the wetting agents used do not lower the viscosity of the emulsion paint. The viscosity of the white dispersion paint is determined after one day with a Brookfield viscometer, spindle # 4 at 100 rpm. The viscosity of the white dispersion paint should not change significantly after addition of the wetting agent.

Oberflächenspannung der WeißdispersionsfarbenSurface tension of the white dispersion paints

Als Maß für die Netzwirkung der Weißdispersionsfarben wird die Oberflächenspannung gemessen. Dazu wird die Weißdispersionsfarbe in einem Gewichtsverhältnis von 1:1 mit Wasser verdünnt und die Oberflächenspannung mit einem Lauda Tensiometer bestimmt, dass nach der Platinringmethode nach ASTM D971 arbeitet. Die Wirksamkeit der verwendeten Netzmittel zeigt sich in einer Erniedrigung der Oberflächenspannung. Je niedriger die Oberflächenspannung der verdünnten Weißdispersionsfarben, des so wirksamer ist die Netzwirkung der verwendeten Produkte.As a measure of the net effect of the white dispersion paints, the surface tension is measured. For this, the white dispersion paint is diluted with water in a weight ratio of 1: 1 and the surface tension is determined using a Lauda Tensiometer, which works according to the platinum ring method according to ASTM D971. The effectiveness of the wetting agents used is reflected in a lowering of the surface tension. The lower the surface tension of the diluted white dispersion paints, the more effective is the net effect of the products used.

Abtönen der DispersionsfarbenTinting the emulsion paints

Zum Einstellen eines bestimmten Farbtons werden den Weißdispersionsfarben Abtönpasten zugesetzt. Für das Ausprüfen der Farbstärke und Kompatibilität von Abtönpasten werden 200 g abgetönte Dispersionsfarbe bestehend aus 98 Gew.-% Weißdispersionsfarbe und 2 Gew.-% einer Blaupigmentpaste in eine Blechdose geben und 60 Sekunden in einem Inkshaker 500 der Fa. Olbrich Know How, Hemer homogenisiert. Die verwendete Blaupigmentpaste hat folgende Zusammensetzung. Tabelle 3: Zusammensetzung der Blaupigmentpaste zum Abtönen der Dispersionsfarben Nr. Komponente Zusammensetzung/Eigenschaft in Gew.-% 1 Wasser 33,5 2 Emulsogen® LCN 118 Dispergiermittel 6,0 3 D-Foam-R C 741 Siliconölentschäumer 0,3 4 Nipacide® BIT 10 W Benzisothiazolinon, Biozid 0,2 5 Polyethylenglykol 300 Feuchthaltemittel 10,0 6 Hostaperm® Blau B2G Phthalocyaninpigment, Color Index PB 15:3 50,0 Summe 100,0 To set a particular hue, tinting pastes are added to the white dispersion paints. For the evaluation of the color strength and compatibility of tinting pastes 200 g of tinted emulsion paint consisting of 98 wt .-% white dispersion paint and 2 wt .-% of a blue pigment paste in a tin can and homogenized for 60 seconds in an Inkshaker 500 from. Olbrich Know How, Hemer , The blue pigment paste used has the following composition. Table 3: Composition of the blue pigment paste for tinting the emulsion paints No. component Composition / property in% by weight 1 water 33.5 2 Emulsogen® ® 118 LCN dispersants 6.0 3 D-Foam-R C 741 Siliconölentschäumer 0.3 4 Nipacide ® BIT 10 W Benzisothiazolinone, biocide 0.2 5 Polyethylene glycol 300 Humectants 10.0 6 Hostaperm ® Blue B2G Phthalocyanine pigment, Color Index PB 15: 3 50.0 total 100.0

Zur Bestimmung der Farbstärke und der Kompatibilität der Farbpaste in der Weißdispersionsfarbe werden die abgetönten Dispersionsfarben nach einem Tag auf einem Prüfkarton mit einer 120 µm Rakel auf einem Filmziehgerät, Modell 509 MC der Fa. Erichsen GmbH, Hemer ausgestrichen. Nach 7 Minuten wird der Rubout-Test auf dem trocknenden Falbfilm in der in der Schrift US-3840383 beschriebenen Weise durchgeführt. Von dem vollständig getrockneten Film werden nach 24 Stunden die farbmetrischen Werte mit einem Konica - Minolta Spektrophotometer Modell CM 3600 bestimmt. Tabelle 4: Eigenschaften der Dispersionsfarben Beispiel Versuch Dichte der Farbe Viskosität Oberflächenspannung Relative Farbstärke Rubout [g/cm3] [mPa·s] [mN/m] [%] 1 (V) Emulsogen LCN 070 1,3276 2133 35,6 54,7 Ja 2 (V) Genapol PF 10 1,3542 2000 36,6 100,8 Nein 3 (V) Genapol PF 20 1,3587 1720 32,6 99,3 Nein 4 (V) Genapol PF 40 1,3594 1780 30,6 100,9 Nein 5 (V) Genapol PN 30 1,3635 2160 29,0 100,0 Nein 6 (V) Genapol EP 2584 1,3515 2290 36,3 86,3 Nein 7 (V) Genapol BE 2410 1,2870 1740 30,4 54,7 Ja 8 Glyzerin + 24 EO + 48 PO 1,3649 2140 29,8 97,5 Nein 9 Butantriol + 24 EO + 48 PO 1,3391 2000 29,6 97,0 Nein 10 Hexantriol + 24 EO + 48 PO 1,3447 2100 30,3 99,2 Nein 11 (V) Ohne Netzmittel 1,2987 1950 39,2 36,6 Ja To determine the color strength and the compatibility of the color paste in the white dispersion paint, the tinted emulsion paints are coated after one day on a test board with a 120 .mu.m knife on a film applicator, model 509 MC Fa. Erichsen GmbH, Hemer. After 7 minutes, the rubout test on the drying Falbfilm in the font US 3840383 described manner performed. From the fully dried film, the colorimetric values are determined after 24 hours with a Konica - Minolta Model CM 3600 spectrophotometer. Table 4: Properties of the emulsion paints example attempt Density of color viscosity surface tension Relative color strength rubout [g / cm 3 ] [MPa.s] [MN / m] [%] 1 (V) Emulsogen LCN 070 1.3276 2133 35.6 54.7 Yes 2 (V) Genapol PF 10 1.3542 2000 36.6 100.8 No 3 (V) Genapol PF 20 1.3587 1720 32.6 99.3 No 4 (V) Genapol PF 40 1.3594 1780 30.6 100.9 No 5 (V) Genapol PN 30 1.3635 2160 29.0 100.0 No 6 (V) Genapol EP 2584 1.3515 2290 36.3 86.3 No 7 (V) Genapol BE 2410 1.2870 1740 30.4 54.7 Yes 8th Glycerol + 24 EO + 48 PO 1.3649 2140 29.8 97.5 No 9 Butantriol + 24 EO + 48 PO 1.3391 2000 29.6 97.0 No 10 Hexane triol + 24 EO + 48 PO 1.3447 2100 30.3 99.2 No 11 (V) Without wetting agent 1.2987 1950 39.2 36.6 Yes

Die erfindungsgemäßen Dispersionsfarben der Beispiele 8 bis 10 zeigen zusammen mit dem Beispiel 5 (V) gegenüber dem Stand der Technik die besten Ergebnisse: Das Netzmittel aus Beispiel 1 (V) neigt deutlich zum Schäumen, was in einer niedrigeren Dichte von etwa 1,33 g/ml und einem höheren Lufteinschluss als bei den Netzmitteln der Beispiele 8 bis 10 resultiert. Die Netzmittel der Beispiele 2 (V) und 6 (V) zeigen eine geringere Netzwirkung und eine höhere Oberflächenspannung von etwa 36 mN/m gegenüber den Netzmitteln in Beispiel 8 bis 10. Die Verwendung der Netzmittel der Beispiele 3 (V) und 4 (V) führt zu einer niedrigeren Viskosität der Dispersionsfarben als bei Verwendung der Netzmittel der Beispiele 8 bis 10. Das Netzmittel des Beispiels 5 (V) zeigt vergleichbare Ergebnisse wie die Netzmittel der Beispiele 8 bis 10, weist aber im Gegensatz zu diesen einen ammoniakalischen Geruch und eine dunkle Farbe auf, während die Netzmittel der Beispiele 8 bis 10 frei von ammoniakalischem Geruch sind und eine helle bis klare Farbe zeigen. Die dunkle Farbe des Netzmittels in Beispiel 5 (V) wird durch das Verwenden von Ethylendiamin als Startmolekül für die Alkoxylierung verursacht. Die Netzmittel der Beispiele 8 bis 10 sind dagegen farblos bis gelblich und sind frei von ammoniakalischem Geruch. Das Netzmittel in Beispiel 7 (V) ist gänzlich ungeeignet, weil die Farbstärke ähnlich wie in Beispiel 1 (V) weit hinter den Farbstärken der Beispiele 8 bis 10 zurück bleibt.The emulsion paints according to the invention of Examples 8 to 10 together with Example 5 (V) show the best results with respect to the prior art: The wetting agent from Example 1 (V) has a marked tendency to foam, resulting in a lower density of approximately 1.33 g / ml and higher air entrapment than the wetting agents of Examples 8-10. The wetting agents of Examples 2 (V) and 6 (V) show a lower net effect and a higher surface tension of about 36 mN / m over the wetting agents in Examples 8 to 10. The use of the wetting agents of Examples 3 (V) and 4 (V The wetting agent of Example 5 (V) shows comparable results to the wetting agents of Examples 8 to 10, but in contrast to these has an ammoniacal odor and a dark color while the wetting agents of Examples 8-10 are free of ammoniacal odor and show a light to clear color. The dark color of the wetting agent in Example 5 (V) is caused by using ethylenediamine as the starting alkoxylation molecule. The wetting agents of Examples 8 to 10, however, are colorless to yellowish and are free of ammoniacal odor. The wetting agent in Example 7 (V) is wholly unsuitable because, similar to Example 1 (V), the tinting strength lags far behind the tints of Examples 8-10.

Claims (13)

  1. The use of compounds of the formula (I)
    Figure imgb0004
     in which
    A is a radical derived from a polyfunctional alcohol or alkanolamine having at least 3 active hydrogen atoms,
    R is a methyl or ethyl radical,
    R' is a hydrogen atom or a methyl, ethyl, propyl, or butyl radical,
    n is an integer from 1 to 250,
    m is an integer from 1 to 500,
    x is less than or equal to the number of active hydrogen atoms in the polyfunctional alcohol or alkanolamine from which A is derived,
    and in which the polyoxyethylene and the polyoxyalkylene groups are arranged blockwise in the order indicated in the formula (I), as deaerating wetting agent and dispersant in emulsion paints comprising water and
    (A) at least one polymer dispersion which comprises homopolymers or copolymers of olefinically unsaturated monomers,
    (B) at least one inorganic white pigment or one inorganic filler,
    (C) at least one organic chromatic pigment or carbon black pigment.
  2. The use as claimed in claim 1, where 0.01 to 10 wt.% of (E) customary auxiliaries used for emulsion paints and selected from the group consisting of wetting agents, dispersants, defoamers, rheological additives, biocides, fungicides, algicides, film-forming assistants, buffer substances such as aqueous sodium hydroxide solution, ammonia solution, amines such as 2-amino-2-methyl-1-propanol, and acids such as sulfuric acid, hydrochloric acid, and acetic acid, are further comprised.
  3. The use as claimed in claim 1 and/or 2, where further 1 to 70 wt.% of (F) further adjuvants selected from the group consisting of inorganic chromatic pigments, silicone resins, potassium silicate, or alkyd resin dispersions are comprised.
  4. The use as claimed in one or more of claims 1 to 3, wherein the olefinically unsaturated monomers are selected from vinyl monomers, aryl-substituted olefins, olefinically unsaturated carboxylic esters, olefinically unsaturated dicarboxylic esters, olefinically unsaturated carboxylic acids and dicarboxylic acids, olefinically unsaturated sulfonic acids and phosphonic acids and alkali metal salts and ammonium salts, olefinically unsaturated amines, ammonium salts, nitriles and amides, and olefins or halogenated olefins having 2 to 8 carbon atoms.
  5. The use as claimed in one or more of claims 1 to 4, wherein A comprises up to 8 active hydrogen atoms.
  6. The use as claimed in one or more of claims 1 to 5, wherein x is 3, 4, 5, or 6.
  7. The use as claimed in one or more of claims 1 to 6, wherein n is an integer from 5 to 100.
  8. The use as claimed in one or more of claims 1 to 7, wherein m is an integer from 10 to 200.
  9. The use as claimed in one or more of claims 1 to 8, where 1 to 75 wt.% of (A) are comprised.
  10. The use as claimed in one or more of claims 1 to 9, where 1 to 70 wt.% of (B) are comprised.
  11. The use as claimed in one or more of claims 1 to 10, where 0.1 to 10 wt.% of (C) are comprised.
  12. The use as claimed in one or more of claims 1 to 11, where 0.05 to 2 wt.% of (D) are comprised.
  13. The use as claimed in one or more of claims 1 to 12, where 20 to 80 wt.% of water are comprised.
EP20120708247 2011-03-16 2012-03-08 Branched polyalkylene glycol ethers as de-airing wetting and dispersing agents for aqueous dispersion colors Not-in-force EP2686390B1 (en)

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